Certain oxime esters and their use as acaricides and in controlling fungi and bacteria

ABSTRACT

COMPOUNDS HAVING THE FORMULA   HAL-CH2-C(-R1)=N-OOC-R2   IN WHICH HAL IS CHLORINE, BROMINE OR IODINE, R1 IS (1) HYDROGEN, (2) LOWER ALKYL, (3) ARYL, (4) NUCLEAR SUBSTITUTED DERIVATIVES THEREOF IN WHICH THE SUBSTITUENTS ARE HALOGEN, NITRO, LOWER ALKYL, OR CYANO AND (5) HALOALKYL, AND R2 IS (1) ARYL, (2) NUCLEAR SUBSTITUTED DERIVATIVES THEREOF IN WHICH THE SUBSTITUENTS ARE HALOGEN, CYANO, NITRO, LOWER ALKOXY, OR LOWER ALKOXY OR LOWER ALKYL, (5) NUCLEAR SUBSTITUTED STYRYL, IN WHICH THE SUBSTITUENTS ARE HALOGEN, CYANO, NITRO, LOWER AKOXY OR LOWER ALKYL, (5) BENZYL, (6) NUCLEAR SUBSTITUTED BENZYL IN WHICH SAID SUBSTITUENTS ARE HALOGEN, CYANO, NITRO, LOWER ALKOXXY OR LOWER ALKYL, (7) PHENETHYL, (8) NUCLEAR SUBSTITUTED PHENETHYL IN WHICH THE SUBSTITUENTS ARE HALOGEN, CYANO, NITRO, LOWER ALKOXY, OR LOWER ALKYL, (9) C CYCLOALKYL HAVING 3 TO 6 CARBON ATOMS, AND (10) FURYL.

United States Patent OflEice 3,732,306 Patented May 8, 1973 CERTAINOXIME ESTERS AND THEIR USE AS ACARICIDES AND IN CONTROLLING FUNGI ANDBACTERIA Arnold D. Gutman, San Rafael, and Don R. Baker,

Pinole, Calif., assignors to Staulfer Chemical Company, New York, N.Y.

No Drawing. Original application July 22, B68, Ser. No. 746,309. Dividedand this application July 2, 1970, Ser. No. 60,961

Int. Cl. C07c 123/00 US. Cl. 260566 AE 12 Claims ABSTRACT OF THEDISCLOSURE Compounds having the formula hal-CH2 O in which hal ischlorine, bromine or iodine, R is 1) hydrogen, (2) lower alkyl, (3)aryl, (4) nuclear substituted derivatives thereof in which thesubstituents are halogen, nitro, lower alkoxy, lower alkyl, or cyano and(5) haloalkyl, and R is (1) aryl, (2) nuclear substituted derivativesthereof in which the substituents are halogen, cyano, nitro, loweralkoxy, or lower alkyl, (3) styryl, (4) nuclear substituted styryl, inwhich the substituents are halogen, cyano, nitro, lower alkoXy or loweralkyl, (5) benzyl, (6) nuclear substituted benzyl in which saidsubstituents are halogen, cyano, nitro, lower alkoxy or lower alkyl, (7)phenethyl, ('8) nuclear substituted phenethyl in which the substituentsare halogen, cyano, nitro, lower alkoxy, or lower alkyl, (9) cycloalkylhaving 3 to 6 carbon atoms, and (10) furyl.

This application is a division of copending application Ser. No.746,309, filed July 22, 1968 and now US. Pat. No. 3,592,920.

This invention relates to novel chemical compounds and to their use asherbicides and acaricides and in controlling fungi and bacteria. Moreparticularly, the chemical compounds are certain keto oxime esters.

The compounds of the present invention are those having the formula inwhich hal is a member selected from the group consisting of chlorine,bromine and iodine, preferably chlorine, R is a member selected from thegroup consisting of (1) hydrogen, (2) lower alkyl, preferably havingfrom 1 to 6 carbon atoms, (3) aryl, preferably phenyl, (4) nuclearsubstituted derivatives thereof in which the substituents are selectedfrom the group consisting of halogen, nitro, lower alkoxy, preferablyhaving from 1 to 4 carbon atoms, more preferably methoxy, lower alkyl,preferably having 1 to 4 carbon atoms, more preferably, methyl, andcyano and (5) haloalkyl, preferably having from 1 to 4 carbon atoms;most preferably chloromethyl, and R isa member selected from the groupconsisting of 1) aryl, preferably phenyl (2) nuclear substitutedderivatives thereof in which the substituents are selected from thegroup consisting of halogen, preferably chlorine and bromine, cyano,nitro, lower alkoxy, preferably having from 1 to 4 carbons, morepreferably methyl, (3)

styryl, (4) nuclear substituted styryl, in which the substituents areselected from the group consisting of halogen, preferably chlorine andbromine, cyano, nitro, lower alkoxy, preferably having 1 to 4 carbonatoms, more preferably methoXy, and lower alkyl, preferably having 1 to4 carbon atoms, more preferably methyl, (5) benzyl, (6) nuclearsubstituted benzyl in which said substituents are selected from thegroup consisting of halogen, preferably chlorine and bromine, cyano,nitro, lower alkoxy, preferably having 1 to 4 carbon atoms, morepreferably methoxy and lower alkyl, preferably having 1 to 4 carbonatoms, more preferably methyl, (7) phenethyl, (8) nuclear substitutedphenethyl in which the substituents are selected from the groupconsisting of halogen, preferably chlorine and bromine, cyano, nitro,lower alkoxy, preferably having 1 to 4 carbon atoms, more preferablymethoxy and lower alkyl, preferably having 1 to 4 carbon atoms, morepreferably methyl, (9) cycloalkyl having 3 to 6 carbon atoms, preferablycyclohexyl, and (10) furyl.

The term nuclear substituted includes both mono and poly substitutionwith the specified substituent.

The term halogen or the prefix halo used in describ ing the compound ofthe present invention encompass chlorine, bromine, iodine, and fluorine.

Representative compounds of this invention are:

1,3-dichloro-2-propanoneoximinobenzoate 1,3-dichloro-Z-propanoneoximinonaphthoate 1,3-dichloro-2-propanoneoximino-p-chlorobenzoate 1,3-dichloro-2-propanoneoximino-3,4-dichlorobenzoate1,3-dichloro-2-propanoneoximino-3,4,5-trirnethoxybenzoate1,3-dichloro-2-propanoneoxirnino-p-bromobenzoate1,3-dichloro-2-propanoneoximino-p-iodobenzate1,3-dichloro-2-propanoneoximino-p-fiuorobenzoate1,3-dichloro-2-propanoneoximino-4-butylbenzoate 1,3-dichloro-2-propanoneoximino-4-cyanobenzoate1,3-dichloro-2-propanoneoximino-4-nitrobenzoate1,3-dichloro-2-propanoneoximino-4-n-butoxybenzoatel,3-dichloro-2-propanoneoximino-cinnamate 1,3-dichloro-2-propanone0ximino-p-chlorocinnamate1,3-dichloro-2-propanoneoximino-3,4-dichlorocinnamate 1,3-dichloro-2-propanoneoximino-3,4,5-trimethoxycinnamate1,3-dichloro-2-propanoneoximino-p-bromocinnamate1,3-dichloro-2-propanoneoximino-p-iodocinnamate1,3-dichloro-2-propanoneoximino-p-fluorocinnamate1,3-dichloro-2-propanoneoximino-4-t-butyl cinnamate 1,3-dich1oro-2-propanoneoximino-4-n-butyoxycinnamate1,3-dichloro-2-propanoneoximino-4-cyanocinnamate1,3-dichloro-Z-propzmoneoximino-4-nitrocinnamate1,3-dichloro=2-propano-neoximino-hydrocinnamate1-chloro-2-propanoneoximinobenzoate 1-chloro-2-octanoneoximinobenzoate1,6-dichloro-2-hexanoneoximinobenzoate1,3-dibromo-2-propanoneoximinobenzoate 1,3-diiodo-2-propanoneoximinobenzoatel-chloro-3-bromo-2-propanoneoximinobenzoate 1-fluoro-2-propanoneoximinobenzoate chloroethanaloximinobenzoatea-chloroacetophenoneoximinobenzoatea-bromo-4-chloro-acetophenoneoximinobenzoatea-chloro-4-nitroacetophenoneoximinobenzoatea-chloro-4-cyanoacetophenoneoximinobenzoatea-chloro-4-methoxyacetophenoneoximinobenzoatea-chloro-4-methylacetophenoneoximinobenzoate The compounds of thepresent invention are particularly useful as acaricides. The compoundsare also useful in inhibiting the growth of bacteria and fungi. Also,the compounds of the present invention find use as herbicides,especially in post-emergent control of weeds.

The compounds of the present invention can be pre pared by reacting acompound of the formula hal-CH:

O=NOH in which ha] and R are as defined before with a compound of theformula II halo- (3-H in which halo is chlorine or'bromine and R is aradical as defined as above.

The above reaction yields compounds of the formula Example 11,3-dichloroacetoneoximino-3-methyl-benzoate 63.5 gms. (0.50 mole)1,3-dichloropropanone, 69.5 gms. 1.00 moles) hydroxylaminehydrochloride, 250 ml. ethanol and ml. of water are combined and heatedunder reflux for four hours. The cooled mixture is poured into 500 ml.of water. The aqueous solutions is extracted with 3100 ml. portions ofchloroform. The chloroform phases are combined and dried with anhydrousMgSO The chloroform is evaporated to give 66.3 g. (93.6% of theory) of1,3-dichloroacetoneoxime,

ClHzC C=NOH ClHzC N =1.5044.

14.2 grns. (0.1 mole) of 1,3-dichloroacetoneoxime prepared according tothe above procedure and 14.4 gms.

(0.093 mole) of m-toluoyl chloride are combined in 200 ml. of benzeneand the mixture is cooled to 15 C. 12.1

gms. (0.12 mole) of triethylamine are added dropwise while keeping thetemperature between 15 20 C. with stirring. The reaction is continuedminutes after the completion of the addition of triethylamine. Themixture is washed twice with water, twice with NaHCO and again twicewith water. The benzene phase is dried with anhydrous MgSO; andevaporated to give 11.1 g. of 1,3- dichloroacetoneoximino-3methylbenzoate,

CH 011120 I? The following is a table of certain selected compounds thatare prepared according to the procedure described hereto. Compoundnumbers are assigned to each compound and are used throughout theremainder of the application.

TABLE I Compound Number Phenyl. 2-cl1loropl1enyl. 4-ch1orophenyL3,4-diehloropheny1. 3-chl0rophenyl.

. 4-bromophenyl. 2-bromophenyl.

methoxyphenyl. 2-methoxyplienyl.

3,4,5-t1'imeth0xyphenyl. 5 4-nitrophenyl.

3-nitrophenyl.

3,5-dinitrophenyl.

4-methylphenyl.

3-metl1ylphenyl.

2methylphenyl.

Styryl.

Benzyl.

Cyelohexyl. a-chlorophenyl. Plienyl.

21 do do do Phenyl.

The following tests illustrate utility of the compounds in controllingfungi and bacteria and as acaricides.

In vitro vial test-This test measures the bactericidal and fungicidalproperties of a compound when in contact with a growing bacterium orfungus. The test is conducted by partially filling two l-ounce vialswith malt broth and one l-ounce vial with nutrient broth. Next, the testcompound is added to the vials at a certain concentration, expressed inparts per million, and mixed with the broth. A water suspension ofspores of the desired fungi or cells of the desired bacteria (oneorganism per vial) is added. The vials are then sealed and incubated forone week; at this time the vials are examined and the results recorded.Table IV shows the results of various compounds tested by the in vitrovial test.

TABLE II Concentration (p.p.m.) which inhibited growth 1 Fungus Igacteria,

Aspergillus Penicillium coccus Compound nz'ger .91). aureus 1 )=Partialcontrol.

acaricides. Young pinto bean plants in the primary leaf stage were usedas the host plants. The young pinto bean plants were infested withseveral hundred mites. Dispersions of candidate materials were preparedby dissolving 0.1 gram in 10 ml. of a suitable solvent, usually acetone.Aliquots of the toxicant solutions were suspended in water containing0.0175 v./v. Sponto 221 an emulsifying agent, the amount of water beingsufficient to give concentrations of active ingredient ranging from0.25% to 0.001%. The test suspensions were then sprayed on the infestedpinto bean plants. After seven days, mortalities of post-embryonic andovicidal forms were determined. The percentage of kill was determined bycomparison with control plants which had not been sprayed with thecandidate compounds. The LD-50 value was calculated using well-knownprocedures. These values are reported under the columns PE and Eggs inTable II.

TAB LE III Acaricidal activity Compound Number PE Eggs 0. O1 0. 03 0. 050. 05 0. 01 0. 03 0. 008 0. 03 0. 01 0. 05 0. 01 0. O5 0. 01 0. 05 0. 050. 05 0. 05 0. 05 0. 05 0. ()5 0. 03 0. 05 0. 03 0. 03 0. 05 0. 05 0.008 0. 05 0. 03 0. 05 0. 03 0. 05 0. 005 0. 03 0. 05 0. 05 0. 03 0. 050. 03 0. 05 0. 03 0. 05 0. 05 0. 05 0. 05 0. 05 0. 05 0. 05 0. 05 0. 050. ()5 O. 05 0. 05 0. 05 0. 05 0. 05 0. 05 0. 05

Various techniques or methods can be employed for contacting acaridswith the compounds. For example, spray formulations can be prepared bydissolving a compound in suitable organic solvent such as toluene,xylene, benzene, and the like, and subsequent dispersion of thissolution in water in the presence of a surface active wetting oremulsifying agent. Another method by which the acaricidal agents of thepresent invention can be applied is in the form of dispersible powders,preferably as homogeneous free-flowing dusts commonly formulated bymixing the active component with finely divided solids or carriers suchas talc, natural clays, diatomaceous earth, various flours such aswalnut shell, wheat and the like. The details of compounding andapplication are well known to those skilled in the art.

As previously stated, the compounds of this invention are useful asherbicides and especially as post-emergence type herbicides. Thepost-emergence herbicide testing procedure is as follows:

Post-emergence herbicide test.-The seeds of crabgrass, watergrass, redoats. Indian mustard, curly dock and pinto bean were planted inindividual rows in Santa Cruz sandy loam soil. After growing for twoweeks under greenhouse conditions, the plates were four to six inchestall. Thereafter, the candidate test compound was applied to the foliageby means of an overhead spray while the fiat moved under the spray on amoving table. A concentration of 0.5% of active compound in the spraywas used at a rate equivalent to approximately 60 lbs./ acre. Two weeksafter treatment, the injury results were recorded and it was determinedthat the compounds of the invention have utility as herbicides,especially postemergence herbicides.

Compound Numbers 1, 4 and 17 were selected for further evaluation andwere found to give generally excellent control at the application rateof 2 pounds per acre of certain weed species as is shown in Table IV.

The compounds of the present invention as post-emergence herbicides andcan be applied in a variety of ways at various concentrations. They maybe combined with suitable carriers and applied as dusts, sprays ordrenches. The amount applied will depend upon the nature of the weeds orplants to be controlled and the rate of application may vary from 1 to80 pounds per acre. One particularly advantageous way of applying thecompounds is as a narrow band along a row crop, straddling the row. Itis not necessary that the phytotoxic compositions be admixed with thesoil particles and these compositions can be applied merely by sprayingor sprinkling the surface of the soil. The phytotoxic compositions ofthis invention can also be applied to irrigation water supplied to thefield to be treated. This method of application permits the penetrationof the compositions into the soil as the water is absorbed therein. Dustcompositions, granular compositions or liquid formulations applied to ofthe soil by conventional means such as discing, dragging the surface ofthe soil can be distributed below the surface or mixing operations.

The phytotoxic compositions of this invention can also contain otheradditaments, for example fertilizers, pesticides and the like, used asadjuvant or in combination with any of the above-described adjuvants.Other phytotoxic compounds useful in combination with the abovedescribedcompounds include for example 2,4-dichlorophenoxyacetic acids, 2,4,5trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and thesalts, esters and amides thereof; triazine derivatives, such as 2,4-bis-(3 methoxypropylamino) 6 methylthio-s-triazine; 2- chloro 4 ethylamino 6isopropylamino-s-triazine, and 2 ethylamino 4 isopropylamino 6methylmercapto-S-triazine, urea derivatives, such as3-(3,4-dichlorophenyl) 1,1 dimethyl urea and 3-(p-chlorophenyl)-l,1-dimethyl urea and acetamides such as N,N-diallyl-achloroacetarnide,N-(a-chloroacetyl)hexamethylene imine, and N,N-diethyl-a-bromacetamide,and the like; benzoic acids such as 3-amino 2,5 dichlorobenzoic and;thiocarbamates, such as S-propyl dipropylthiocarbamate; S- ethyldipropyl-thiocarbamate, S-ethyl cyclohexyl-ethylthiocarbamate, S-ethylhexahydro 1H azepine-l-carbothioate and the like. Fertilizers useful incombination with the active ingredients include for example ammonumnitrate, urea and super-phosphate. Other useful additaments includematerials in which plant organisms take root and grow such as compost,manure, humus, sand and the like.

The concentration of a compound of the present invention, constitutingan effective amount in the best mode of administration in the utilitydisclosed is readily determinable by those skilled in the art.

phenyl.

r 7. We claim: I 1.- A compound having the formula o=N -0-hm in whichhal is selected from the group consisting-of chlorine, bromineandiodine; R is monohaloloweralkyl; and R is phenyl of nuclearusubstitutedphenyl wherein the substituents are selected from the group consistingof halogen; nitro, lower alko'xy} lower alkyl; and cyano.

2. The compound of claim- 1 inwhich R is chloromelthyl and-R is phenyllv 3. 'The compound of elaimvl in which R 'is chloro methyl and R is ahalogen substituted phenyl.

4. The compound of claim 3 in which-R is 3-chloro- 5. The compound ofclaim 3' in which R is 4-chlorophenyl. 6. The compound ofclaim-3 inwhich R**- is 3,4-dichlorophenylvh U .Li.

7. The compound of claim 3 in which R is 2-bromophenylt 12. The compoundof claim 11in which R is 4-methyl phenyl. 1 a

'- References Cited UNITED .STATES PATENTS 3,063,823 11/1962 Kiihle eta1. 260566 AE', 3,169,989 2/1965 Tieman 6:61. 260566 AE 3,655,761 4/1972Gutman 260-566 AB BERNARD HELFIN, Primary Examiner G. A. SCHWARTZ,Assistant Examiner

